Cosmetic compositions containing oxazoline functionalized polymers and polyamine compounds

ABSTRACT

Disclosed are compositions, systems and methods for treating keratinous fibers such as hair. The compositions and systems comprise an oxazoline functionalized polymer and a polyamine compound. The compositions and methods are employed to improve the quality of the keratinous fibers.

FIELD OF THE INVENTION

The present invention relates to compositions, agents, and methods fortreating keratinous fibers. More particularly, the present inventionrelates to keratinous fiber treatment compositions that can repair orprevent/minimize damaging effects on keratinous substrates caused byextrinsic and intrinsic factors by providing desirable or improvedquality and conditioning, hydrophobicity, repair, and improvedmechanical properties of the keratinous fibers, such as hair.

BACKGROUND OF THE INVENTION

The appearance and/or condition of keratinous substrates, for example,keratinous fibers such as hair, skin, nails, and lips, are oftenaffected by both extrinsic and intrinsic factors such as aging. Inparticular, when keratinous substrates are exposed to environmentalconditions, for example, high or low humidity or to ultravioletradiation from the sun, these substrates can lose many of theirdesirable properties and even become damaged. Keratinous substratescomprising keratinous fibers, especially hair, are constantly exposed toharsh extrinsic conditions, such as sun, chemical damage, e.g., fromdetergents in shampoos, bleaching, relaxing, dyeing, and permanentwaving, heat, e.g., from hair dryers or curlers, and mechanical stressor wear, e.g., from brushing or grooming activities. In addition, anytype of hair can diminish in quality and/or quantity over time by ageand/or due to factors such as natural greasiness, sweat, shedded skincells from the scalp, pollution, dirt, and extreme humidity conditions.

The above-described factors can result in thinning hair and/or hairbreakage and/or harm the visual appearance and the feel of the hair, andlead to lank body and decreased volume. For example, hair can dry outand lose its shine or color or become frizzy and less manageable underlow and high humidity conditions. Under low humidity conditions, haircan dry out and dried-out hair tends to be less shiny and more brittle.Conversely, under high humidity conditions, hair tends to absorb water,causing hair to lose its shape and become unmanageable and unattractive.In addition, hair fibers can become less strong, thereby breaking easilyunder stress such as stress induced by pulling, brushing, or combingactivities. Furthermore, hair can lose its desirable attributes due tophysical stress on the hair such as brushing and application of heat.The magnitude of the consequences of these factors is variable,depending on, for example, the quality of the hair, length, style, andenvironmental factors. As such, these factors generally result in damageto the keratinous fibers, either by affecting protective materials onthe surface of the hair (the cuticle), or by altering the hair fiberinternally (the cortex).

More specifically, extrinsic conditions may strip protective materialsfrom the surface of the hair, and/or they may disrupt the organizedstructure of the hair fibers, called the a-structure, which may beaccompanied by a decrease in the tensile strength. Such damage to hairby extrinsic factors is more evident the further the hair fiber hasgrown from the root, because the hair has been exposed longer to suchextrinsic factors. In effect, the hair has what may be called a “damagehistory” as it grows, i.e., the further from the root, the lower thetensile strength and the greater the breakdown in a-structure that hasoccurred. As a result, consumers continue to seek products such as haircare and hair cosmetic compositions which protect and enhance theappearance of hair as well as reduce the deleterious effects of adverseenvironmental conditions, photo-damage, and physical stress. Consumersalso desire to use hair chemical treatments such as hair dyes, hairrelaxers, perm and wave treatments, hair bleaches/lighteners andhighlighting treatments that are less damaging to the hair.

Morphologically, a hair fiber contains four structural units: cuticle,cortex, medulla, and intercellular cement. The cuticle layers arelocated on the hair surface and consist of flat overlapping cells(“scales”). These scales are attached at the root end and point towardthe distal (tip) end of the fiber and form layers around the haircortex. The cortex comprises the major part of the hair fiber. Thecortex consists of spindle-shaped cells, or macrofibrils, that arealigned along the fiber axis. The macrofibrils further consist ofmicrofibrils (highly organized protein units) that are embedded in thematrix of amorphous protein structure. The medulla is a porous region inthe center of the fiber. The medulla is a common part of wool fibers butis found only in thicker human hair fibers. Finally, the intercellularcement is the material that binds the cells together, forming the majorpathway for diffusion into the fibers.

The mechanical properties of hair are determined by the cortex. Atwo-phase model for the cortex organization has been suggested.Milczarek et al, Colloid Polym. Sci., 270, 1106-1115 (1992). In thismodel, water-impenetrable microfilaments (“rods”) are oriented parallelwith the fiber axis. The microfilaments are embedded in awater-penetrable matrix (“cement”). Within the microfilaments, coiledprotein molecules are arranged in a specific and highly organized way,representing a degree of crystallinity in the hair fiber.

Similar to other crystalline structures, hair fibers display a distinctdiffraction pattern when examined by wide-angle X-ray diffraction. Innormal, non-stretched hair fibers this pattern is called an“alpha-pattern”. The alpha-pattern or a-structure of hair ischaracterized by specific repeated spacings (9.8 Å, 5.1 Å, and 1.5 Å).All proteins that display this X-ray diffraction pattern are calleda-proteins and include, among others, human hair and nails, wool, andporcupine quill. When the hair fiber is stretched in water, a new X-raydiffraction pattern emerges that is called a “β-pattern”, with newspacings (9.8 Å, 4.65 Å, and 3.3 Å).

Damage to hair may occur in the cuticle and/or the cortex. When normalhair is damaged by heat, chemical treatment, UV radiation, and/orphysical/mechanical means, myriad chemical and physical changes areinduced in the hair. For example, these damaging processes have beenknown to produce removal or damage to cuticle scales or to cleave thethioester linkage holding the hydrophobic 18-methyl eicosanoic acid(“18-MEA”) layer to hair. Thus, it is commonly observed that undamagedhair exhibits significant hydrophobic character, whereas damaged hairshows significant hydrophilic character due to the removal of surfacelipids.

There is a need, therefore, for cosmetic products that are useful inprotecting the chemical and physical structure of keratinous fibers fromharsh extrinsic conditions and restoring the hair's physical propertiesto undamaged states following damage by extrinsic conditions. Moreparticularly, there is a need to find materials or compositions ormethods that can provide a protective barrier and/or treatment to hairto protect it at the cortex. Such a protective barrier or treatmentshould not be easily transferred from the substrate over time by normaleveryday activity. Non-transfer, wash or water-resistant cosmetic, hairand skin care compositions are sought which have the advantage offorming a deposit which does not undergo even partial transfer to thesubstrates with which they are brought into contact (for example,clothing). It is also desirable to have compositions that do not easily“run off” or wash off the skin and lips when exposed to water, rain ortears. Accordingly, a product that imparts a protective barrier to thesubstrate that also is shampoo, wash or water/humidity resistant andnon-transferable would be of benefit to the area of cosmetic products.As such, makers of cosmetic products such as hair and skin care productscontinue to seek materials and ingredients that can provide suchbenefits. At the same time, long lasting benefits or durability of thesebenefits are also desirable.

In addition, in today's market, many consumers prefer the flexibility ofhaving products that can be used on hair or skin on different ways.Methods for caring for or non-permanent shaping of keratinous fibersinclude, for example, brushing, teasing, braiding, the use of hairrollers, and heat styling, optionally with a commercially available haircare and styling products. Non-limiting examples of heat styling includeblow drying, crimping, curling, and straightening methods using elevatedtemperatures (such as, for example, setting hair in curlers and heating,and curling with a curling iron and/or hot/steam rollers and/or flatiron).

There is a need, therefore, for materials, compositions, treatmentsystems, and methods that result in hair with improved quality or thatis less damaged when the hair is exposed to adverse environmental andphysical factors and/or when chemically treated. As such, it is alsoadvantageous to find a means for treating damaged keratinous fibers byrepairing them, that is to say by intrinsically improving the conditionof the keratinous fibers, reducing and/or preventing breakage of thekeratinous fibers. At the same time, it is desirable that saidmaterials, compositions, treatment systems, and methods provide durableor long-lasting caring and repair benefits to hair.

To achieve at least one or more of these and other advantages, thepresent disclosure provides methods of protecting and/or repairingkeratinous substrates, for example keratinous fibers chosen from hair,eyelashes and eyebrows, from extrinsic damage, for example caused byheating, UV radiation, chemical treatment or other harsh treatment, byapplying to or contacting said keratinous fibers with compositions thatinclude at least one oxazoline functionalized polymer and at least onepolyamine compound in various combinations thereof in amounts effectiveto impart hydrophobicity or increased hydrophobicity to the fiber aswell as repair or reduce/prevent damage to or to prevent/minimizebreakage of or improve the quality and condition of the keratinousfiber.

Another subject of the invention is the use of the combination at leastone oxazoline functionalized polymer and at least one polyamine compoundto improve the condition of the keratinous fibers and/or to repairdamaged keratinous fibers and/or to prevent or reduce breakage ofkeratinous fibers.

BRIEF SUMMARY OF THE INVENTION

According to one embodiment, the disclosure relates to compositions fortreatment of keratinous fibers comprising at least one oxazolinefunctionalized polymer and at least one polyamine compound.

According to a further embodiment, the disclosure relates to methods oftreating keratinous fibers, the methods comprising applying ontokeratinous fibers, a treatment composition(s) or system comprising atleast one oxazoline functionalized polymer and at least one polyaminecompound.

In yet further embodiments, the disclosure relates to systems fortreating keratinous fibers comprising one or two separately-containedtreatment compositions, the system including:

-   -   (a) at least one oxazoline functionalized polymer; and    -   (b) at least one polyamine compound;

-   with the proviso that components (a) and (b) are either (i):    contained in separate treatment compositions; or (ii) contained    together in one treatment composition.

According to a further embodiment, the disclosure relates to methods oftreating keratinous fibers, comprising applying to the fibers, systemscomprising each of the following components, together or separately, inone or two treatment compositions:

-   -   (a) at least one oxazoline functionalized polymer; and    -   (b) at least one polyamine compound;

-   with the proviso that components (a) and (b) are each contained in    two separate treatment compositions or are contained together in one    treatment composition.

In various embodiments, the at least one oxazoline functionalizedpolymer of the compositions, systems, kits, and methods of the presentinvention may be chosen from a waterborne crosslinker polymer, a granuletype, and a mixture thereof.

In various embodiments, the at least one polyamine compound of thecompositions, systems, kits, and methods of the present invention may bechosen from non-alkoxylated polyamines, alkoxylated polyamines, or amixture thereof.

In a further embodiment, the disclosure relates to a kit or an articleof manufacture comprising a kit for treating hair comprising one or twoseparately contained compositions, wherein the compositions include thefollowing components:

-   -   (a) at least one oxazoline functionalized polymer; and    -   (b) at least one polyamine compound;

-   with the proviso that components (a) and (b) are each contained in    two separate treatment compositions or are contained together in one    treatment composition.

Other features and advantages of the present invention will be apparentfrom the following more detailed description of the exemplary embodimentwhich illustrates, by way of example, the principles of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients and/or reaction conditionsare to be understood as being modified in all instances by the term“about,” meaning within 10% of the indicated number (e.g. “about 10%”means 9%-11% and “about 2%” means 1.8% -2.2%).

The articles “a” and “an,” as used herein, mean one or more when appliedto any feature in embodiments of the present invention described in thespecification and claims. The use of “a” and “an” does not limit themeaning to a single feature unless such a limit is specifically stated.The article “the” preceding singular or plural nouns or noun phrasesdenotes a particular specified feature or particular specified featuresand may have a singular or plural connotation depending upon the contextin which it is used. The adjective “any” means one, some, or allindiscriminately of whatever quantity.

“Active material” as used herein with respect to the percent amount ofan ingredient or raw material, refers to 100% activity of the ingredientor raw material.

As used herein, the terms “applying a composition onto keratin fibers”and “applying a composition onto hair” and variations of these phrasesare intended to mean contacting the fibers or hair, with at least one ofthe compositions of the invention, in any manner.

“At least one,” as used herein, means one or more and thus includesindividual components as well as mixtures/combinations.

The term “comprising” (and its grammatical variations) as used herein isused in the inclusive sense of “having” or “including” and not in theexclusive sense of “consisting only of.”

The mole ratio as used herein in the present invention is based on thenumber of functional amino groups of the polyamine compound to thenumber of functional oxazoline groups of the oxazoline functionalizedpolymer.

“Conditioning,” as used herein, means imparting at least one ofcombability, manageability, moisture-retentivity, luster, shine,softness, and body to the hair.

“Durable conditioning,” as used herein, means that, following at leastone shampoo/washing/rinsing after treatment of keratinous fibers such ashair with the compositions of the present disclosure, treated hair stillremains in a more conditioned state as compared to untreated hair. Thestate of conditioning can be evaluated by measuring and comparing, theease of combability of the treated hair and of the untreated hair interms of ease of combing and/or the substantivity of the conditioningagent on the hair and/or the hydrophobicity of hair which can beassessed by contact angle measurements (spread of a water droplet on thesurface of the hair).

“Durable hydrophobicity,” as used herein, means that, following at leastone shampoo/washing/rinsing after treatment of keratinous fibers such ashair with the compositions of the present disclosure, treated hairexhibits significant hydrophobic properties as compared to untreatedhair or to hair treated with a non-inventive/comparative composition ormaterial. The state of hydrophobicity of hair can be assessed by contactangle measurements (for example, by the spread of a water droplet on thesurface of the hair). Durable hydrophobicity as used herein can alsorefer to durable frizz control, i.e., the frizziness of hair iscontrolled even under environmental humidity and/or temperature changes.

“Heating” refers to the use of elevated temperature (i.e., above roomtemperature such as at or above 30° C.). In one embodiment, the heatingin accordance with the present invention may be provided by directlycontacting the keratinous fibers with a heat source, e.g., by use of aheating device on the keratinous fibers. Non-limiting examples ofheating devices and methods to contact the fibers include employing flatironing and curling devices using elevated temperatures (such as, forexample, setting hair in curlers and heating, and curling with a curlingiron and/or hot rollers). In another embodiment, the heating inaccordance with the present invention may be provided by heating the atleast one keratinous fiber with a heat source which may not directlycontact the at least one keratinous fiber. Non-limiting examples of heatsources which may not directly contact the at least one keratinous fiberinclude heating lamps, blow dryers, hair dryers, hood dryers, heatingcaps, and steamers.

“A heat-activated” composition, as used herein, refers to a compositionwhich, for example, imparts to at least one keratinous substrate such asa keratinous fiber, a property or a benefit or coating or film that isdifferent or improved over the same composition or coating or film whichis not heated during or before or after application of the composition.One example includes a composition which imparts better break stressand/or toughness property to at least one keratinous fiber better thanthe same composition which is not heated during or before or afterapplication. Another example includes a composition that forms a coatingor film on the keratinous fiber when the fiber is heated or exposed toelevated temperatures. Another example includes a composition that formsa coating or film on the keratinous fiber and upon exposure or heatingof the treated fiber to heat, imparts one or more additional benefits tothe fibers such as hydrophobicity or improved hydrophobicity or longlasting hydrophobicity even after exposure of the fibers to highhumidity conditions or such as hair manageability or frizzcontrol/improved frizz control.

“High humidity,” as defined herein, refers to atmospheric humidity above40%.

“Homogeneous” means having the visual appearance of being substantiallyuniform throughout, i.e., visually appears as a single-phase emulsionand/or dispersion.

“Keratinous fiber,” as used herein, includes, human keratinous fibers,and may be chosen from, for example, hair, such as hair on the humanhead, or hair comprising of eyelashes or hair on the body. “Keratinousfiber” as used herein can also refer to keratinous substrates.

The term “style” or “styling” as used herein includes shaping,straightening, curling, or placing a keratin fiber such as hair, in aparticular arrangement, form or configuration; or altering the curvatureof a keratinous fiber or other substrate; or re-positioning a keratinfiber or other substrate to a different arrangement, form orconfiguration; or providing/maintaining a hold to the shape orconfiguration of the keratin fiber. In some embodiments, the hold to theshape of configuration of the fiber may be expressed as an improvedbending force property.

The term “treat” (and its grammatical variations) as used herein refersto the application of the compositions of the present invention ontokeratinous substrates such as keratinous fibers or hair or skin or tocontacting said keratinous substrates with the compositions of thepresent invention.

The term “repair” (and its grammatical variations) as used herein meansthat the damaged keratinous fibers such as hair fibers followingtreatment with the compositions of the present disclosure showed animprovement in tensile properties or strength which are similar to thatof natural undamaged hair. The improvement in tensile properties can bedetermined or assessed by any available means such as by mechanicaltests of the fibers and/or by consumer and sensory evaluations ofperceivable fiber strengthening and/or physical attributes which have apositive impact on fiber mechanical properties. The term “wash cycle” asused herein, refers to a step or process of washing keratinous fibersand may include treating the fibers with a surfactant-based product(e.g., shampoo or conditioner or body wash) then washing or rinsing thefibers with water. The term “wash cycle” may also include washing orrinsing the fibers with water.

As used with regard to the present disclosure, an “system” for treatingkeratinous fibers as described herein refers to a combination of atleast two compositions that are intended to be used together, e.g.simultaneously or subsequently with application of one followingapplication of another. For example, a hair treatment system fortreating the hair may comprise application of one treatment compositionto the hair, followed by application of a second treatment compositionto the hair.

Referred to herein are trade names for materials including, but notlimited to polymers and optional components. The inventors herein do notintend to be limited by materials described and referenced by a certaintrade name. Equivalent materials (e.g., those obtained from a differentsource under a different name or catalog (reference number) to thosereferenced by trade name may be substituted and utilized in the methodsdescribed and claimed herein.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages are calculated based on the total weight of acomposition unless otherwise indicated. All component or compositionlevels are in reference to the active level of that component orcomposition, and are exclusive of impurities, for example, residualsolvents or by-products, which may be present in commercially availablesources.

It is an object of the present invention to provide materials andcompositions and methods which provide both a protective coating orbarrier or repairing treatment onto keratinous fibers such as hair andwhich impart native/undamaged physical properties—such as cortex repair,strength, less breakage, hydrophobicity, ease of combing, conditioning,anti-frizz, etc.—to hair, in particular, damaged hair, as well as impartdurable or long lasting physical properties mimicking natural/undamagedhair to damaged hair.

It is also an object of the present invention to provide materials andcompositions and methods which protect or repair a keratinous fiberchosen from hair comprising applying to the keratinous fiber thecomposition(s) or system(s) of the present invention in an amounteffective to protect or repair said keratinous fiber before or during orafter chemically treating the hair (e.g., dyeing the hair usingpermanent, semi-permanent or demi-permanent dyeing compositions,bleaching/lightening or lifting the color of hair by chemical oxidizingagents, perming the hair using chemical reducing/oxidizing agents,relaxing the hair using lye and no-lye compositions, straightening thehair using chemical straightening agents).

As such, it is desirable to formulate hair repair strategies to addressthe need for both surface and cortex repair. It has been surprisinglyand unexpectedly discovered that compositions and systems containing thecombination of oxazoline functionalized polymers and polyaminecompounds, when applied to keratinous fibers such as hair, enhance theproperties of hair wherein the combination controls the frizziness ofhair, increases the conditioning effect (e.g., smoothness, less damagedfeel), increases the humidity resistance or hydrophobicity of hair andameliorates the condition of hair, especially damaged hair, by improvingthe appearance and quality of hair (for example, smoother feel, softerfeel, less damaged feel, more discipline). Thus, the compositions andsystems of the present disclosure can provide a cosmetic treatment suchas hair care, hair treatment, and hair styling/shaping products suchthat the quality of the hair is improved or restored resulting insignificantly less frizzy hair, better cosmeticities, feel andappearance, durable hydrophobicity or frizz control, durableconditioning, and less damaged condition of the hair.

The present disclosure relates to compositions for treatment ofkeratinous fibers comprising at least one oxazoline functionalizedpolymer and at least one polyamine compound.

In an embodiment, the mole ratio of the oxazoline group(s) of the atleast one oxazoline functionalized polymer to the amino group(s) of theat least one polyamine compound is greater than 1.

In an embodiment, the at least one oxazoline functionalized polymer ischosen from waterborne crosslinker polymers such as acrylic-basedoxazoline functionalized polymers and styrene/acrylic-based oxazolinefunctionalized polymer, the granule type, and a mixture thereof.

In an embodiment, the at least one oxazoline functionalized polymer ischosen from 2-Propenoic acid, 2-methyl-, methyl ester, polymer with4,5-dihydro-2-(1-methylethenyl)oxazole and ethyl 2-propenoate withformula: (C₆—H₉—N—O.C₅—H₈—O₂.C₅—H₈—O₂)_(x) (EPOCROS WS-300), anoxazoline functionalized polymer commercially available as EPCROSWS-500, styrene.butylacrylate.2-isopropenyl-2-oxazoline.divinyl benzenecopolymer with formula: (C₇—H₁₂—O₂.C₈.C₁₀-H₁₀.—C₆—H₉—N—O)_(x) (EPOCROSK-2020-E AND EPOCROS K-2030-E), a granule type (EPOCROS RPS-1 005) and amixture thereof.

In an embodiment, the at least one oxazoline functionalized polymer is awaterborne crosslinker polymer chosen from an acrylic-based oxazolinefunctionalized polymer such as 2-Propenoic acid, 2-methyl-, methylester, polymer with 4,5-dihydro-2-(1-methylethenyl)oxazole and ethyl2-propenoate (EPOCROS WS-300), and an oxazoline functionalized polymercommercially available as EPCROS WS-500.

In an embodiment, the at least one oxazoline functionalized polymer is awaterborne crosslinker polymer chosen from styrene/acrylic-basedoxazoline functionalized polymer such asstyrene.butylacrylate.2-isopropenyl-2-oxazoline.divinyl benzenecopolymer (EPOCROS K-2020-E AND EPOCROS K-2030-E).

In an embodiment, the polyamine compound is chosen from non-alkoxylatedpolyamines.

In various embodiments, the polyamine compound is a non-alkoxylatedpolyamine chosen from polyvinylamines, aminated polysaccharides, aminesubstituted polyalkylene glycols, amine substituted polyacrylatecrosspolymers, amine substituted polyacrylates, amine substitutedpolymethacrylates, amine substituted polyesters, polyamino acids,polyalkylamines, diethylene triamine, triethylenetetramine, spermidine,spermine, aminosilicones having at least two amino groups, and a mixturethereof.

In an embodiment, the polyamine compound includes non-alkoxylatedpolyamines such as polyvinylamines.

In an embodiment, the polyamine compound is vinlyamine/vinylformamidecopolymer.

In an embodiment, the polyamine compound is chosen from polyalkylamines.

In an embodiment, the polyamine compound is chosen from alkoxylatedpolyamines.

In various embodiments, the polyamine compound is an alkoxylatedpolyamine chosen from tetradecyloxypropyl-1,3-diaminopropane; a C12-14alkyl oxypropyl-1,3-diaminopropane; a C12-15 alkyloxypropyl amine,diamine alkoxylated polyamine compounds, triamine alkoylated polyaminecompounds, and a mixture thereof.

In an embodiment, the compositions and systems of the present inventioncontain:

-   -   at least one oxazoline functionalized polymer present in a        concentration, by weight, of from about 0.5% to about 10%, or        such as from about 0.7% to about 5%, based on the total weight        of the composition; and    -   at least one polyamine compound present in a concentration, by        weight, of from about 0.003% to about 15% or from about 0.004%        to about 5%, based on the total weight of the composition.

In an embodiment the mole ratio of the oxazoline group(s) of the atleast one oxazoline functionalized polymer to the amino group(s) of theat least one polyamine compound is from between about 1:80 to about80:1.

In an embodiment the mole ratio of the oxazoline group(s) of the atleast one oxazoline functionalized polymer to the amino group(s) of theat least one polyamine compound is greater than 1.

In an embodiment the mole ratio of the oxazoline group(s) of the atleast one oxazoline functionalized polymer to the amino group(s) of theat least one polyamine compound is less than 1.

In an embodiment, the mole ratio of the oxazoline group(s) of the atleast one oxazoline functionalized polymer to the amino group(s) of theat least one polyamine compound is from between about 80:1 to about 1:80or from about 70:1 to about 1:70 or from about 60:1 to about 1:60 orfrom about 50:1 to about 1:50 or from about 60:1 to about 1:60 or fromabout 70:1 to about 1:1 or from about 1:1 to about 1:70 or from about60:1 to about 1:1 or from about 1:1 to about 1:60 or from about 50:1 toabout 1:1 or from about 1:1 to about 1:50 or from about 40:1 to about1:1 or from about 1:1 to about 1:40 or from about 30:1 to about 1:1 orfrom about 1:1 to about 1:30 or from about 20:1 to about 1:1 or fromabout 1:1 to about 1:20 or from about 15:1 to about 1:1 or from about1:1 to about 1:15 or from about 10:1 to about 1:1 or from about 1:1 toabout 1:10 or from about 65:1 to about 1.5:1 or is at about 75:1, 70:1,64:1, 50:1, 45:1, 40:1, 35:1, 30:1, 28:1, 26:1, 251, 22:1, 20:1, 18:1,16:1, 15:1, 12:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1.5:1,1:1.5, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:12, 1:14, 1:15,1:16, 1:18, 1:20, 1:22, 1:24, 1:25, 1:26, 1:28, 1:30, 1:35, 1:40, 1:45,1:50, 1:55, 1:60, 1:64, 1:65, 1:70, or 1:75, including ranges orsub-ranges there between or including all ranges with any of theseamounts being endpoints. Preferably, the mole ratio of the oxazolinegroup(s) of the at least one oxazoline functionalized polymer to theamino group(s) of the at least one polyamine compound is from betweenabout 40:1 to about 2:1 or about 20:1 to about 5:1, including ranges orsub-ranges there between.

In an embodiment the weight proportion of the at least one oxazolinefunctionalized polymer to the at least one polyamine compound is greaterthan 1.

In an embodiment the weight proportion of the at least one oxazolinefunctionalized polymer to the at least one polyamine compound is lessthan 1.

In an embodiment, the compositions and systems of the present inventioninclude amounts of each of the oxazoline functionalized polymer and thepolyamine compound sufficient to impart to the keratinous fibers afterapplication thereto, one or more of hydrophobicity, manageability, andfrizz control.

In an embodiment, the hydrophobicity imparted to the keratinous fibersincludes a contact angle of greater than 85° or greater than 90°.

In an embodiment, the methods of the present invention involve applyingthe composition of the present invention onto hair, followed by heatingthe hair at a temperature from between above room temperature and about250° C. Said method imparts to the hair after application thereto, oneor more of hydrophobicity, manageability, and frizz control.

In an embodiment, the methods of the present invention impart ahydrophobicity or improved hydrophobicity to the hair resulting in acontact angle of greater than 85°.

In an embodiment, the methods of the present invention providehydrophobicity or improved hydrophobicity to the hair that confers highhumidity curl retention after a period of exposure to humidity rangingfrom about 40% to 90%.

In various embodiments, the hydrophobicity imparted to the hair isdurable, i.e., the hair remains hydrophobic even after one or more washcycles. The present invention also relates to systems for treating akeratinous fiber comprising one or two separately-contained treatmentcompositions, the system including:

-   -   (a) at least one oxazoline functionalized polymer; and    -   (b) at least one polyamine compound;

-   with the proviso that either (a) and (b) are each contained in two    separate treatment compositions or (a) and (b) are contained in one    treatment composition; and

-   wherein when (a) and (b) are combined, the mole ratio of the    oxazoline group(s) of the at least one oxazoline functionalized    polymer to the amino group(s) of the at least one polyamine compound    is greater than 1 or is greater than 2 or ranges from between about    40:1 to about 2:1.

In an embodiment, the composition of the present invention comprises twoseparately contained compositions:

-   (1) a first treatment composition containing: at least one oxazoline    functionalized polymer in an amount, by weight, of from about 0.1%    to about 20%, or from about 0.5% to about 10%, or from about 0.7% to    about 5%, based on the total weight of the first treatment    composition; and at least one solvent; and-   (2) a second treatment composition containing: at least one    polyamine compound, in an amount, by weight, of from about 0.04% to    about 20%, or from about 0.05% to about 15%, or from about 0.09% to    about 10%, based on the total weight of the second treatment    composition; and at least one solvent;-   wherein upon mixing (1) and (2) or upon applying (1) and (2) in a    sequential or layer by layer manner onto keratinous fibers, the mole    ratio of the oxazoline group(s) of the at least one oxazoline    functionalized polymer to the amino group(s) of the at least one    polyamine compound ranges from about 1:80 to about 80:1.

In one embodiment, the present invention relates to a method of treatingkeratinous fibers, wherein the method is a two-step process comprisingthe steps of: applying the above-described first treatment compositiononto the fibers; and applying the above-described second treatmentcomposition onto the fibers; and optionally, heating the fibers at atemperature above room temperature; wherein the keratinous fibersinclude hair.

In an embodiment, the composition of the present invention comprises onetreatment composition containing: at least one oxazoline functionalizedpolymer in an amount, by weight, of from about 0.7% to about 5%, basedon the total weight of the treatment composition; at least one polyaminecompound in an amount, by weight, of from about 0.09% to about 3%, basedon the total weight of the treatment composition; and at least onesolvent; wherein the mole ratio of the oxazoline group(s) of the atleast one oxazoline functionalized polymer to the amino group(s) of theat least one polyamine compound ranges from about 1:80 to about 80:1. Inone embodiment, the present invention relates to a method of treatingkeratinous fibers, comprising applying the treatment composition ontothe fibers; wherein the keratinous fibers include hair; and optionally,heating the fibers at a temperature above room temperature.

Without being bound to any one theory, it is believed that the oxazolinefunctionalized polymers and polyamine compounds, react with each otherand to the keratinous substrate via crosslinking reactions when thepolymers or compositions containing the polymers are applied ontokeratinous substrates such as hair. It is also believed that heatactivation or exposing a keratinous substrate such as hair that has beencontacted with the compositions or oxazoline functionalized polymers andpolyamine compounds of the invention to heat or temperatures above roomtemperature enhance the kinetics of the crosslinking reactions, therebyresulting in decreasing the time required to impart cosmetic andhydrophobicity/manageability/repair attributes to the hair. It is alsobelieved that heat activation improves the adhesion and cohesionproperties of films or coatings formed on the hair. The improvedadhesion and cohesion properties result in long-lasting benefits to thehair that withstand shampooing or washing.

The present invention is thus directed to compositions, methods, andsystems employing of oxazoline functionalized polymers and polyaminecompounds in various combinations thereof, which provide a durable orlong-lasting coating on the surface of damaged keratinous substratessuch as hair fibers, provide mechanical strength to the fibers thatleads to repaired/reinforced fibers that are able to withstandday-to-day grooming, and provide hydrophobicity/conditioning/combabilityproperties to the keratinous substrates, such as hair fibers.

Oxazoline Functionalized Polymer

The at least one oxazoline functionalized polymer of the presentinvention is a reactive polymer.

As used herein, the term “reactive polymer” is intended to mean anypolymer having at least one moiety or chemical functional group whichcan chemically react with another substance or compound or polymer.

As used herein, the term “polymer” here means a molecule havingrepeating units. Preferably, the polymers for use in the compositions ofthe present invention have a molecular weight of more than 5000, inparticular, at least 10,000 (g/mole) and with melting temperature, Tg (°C.) ranging from about −50° C. to about 150° C.

Thus, in accordance with the invention, the oxazoline funtionalizedpolymer which is a reactive polymer has at least one moiety or chemicalfunctional group (in this case, an oxazoline group) which can chemicallyreact with the chemical functional group of another substance orcompound or polymer. Such reactions can occur by ring-opening reactions(e.g., amide ester covalent bonding). These reactions can also result inthe formation of a film or coating.

The reactive polymer is also capable of forming at least one covalentbond with keratin fibers such as hair. Thus, the reactive polymerpreferably has at least one chemical functional group which can form atleast one covalent bond with at least one functional group on keratinfibers. As the functional group on the keratin fibers, mention may bemade of, for example, —SH, —OH, —COON, and —NH2.

The chemical functional group may react with the functional group onkeratin fibers, either spontaneously or via an activator chosen fromtemperature, pH, at least one co-reagent, and at least one catalystchosen from chemical and biochemical catalysts, for instance, an enzyme.

The polymers may be in any type of topology chosen from linear,branched, starburst and hyperbranched (for example, dendrimers) chains,and block, random, and alternating chains. The chemical functionalgroups may be naturally present on the polymer chain, at the end of thechain, grafted along the main chain or the secondary chains, or on thebranches of starburst or hyperbranched polymers.

In one embodiment, the reactive polymer may contain two identical ordifferent chemical functional groups.

Thus, in accordance with the invention, the oxazoline funtionalizedpolymer which is a reactive polymer has at least one moiety or chemicalfunctional group (in this case, an oxazoline group) which can chemicallyreact with at least one functional group on keratin fibers. As thefunctional group on the keratin fibers, mention may be made of, forexample, —SH, —OH, —COOH, and —NH2.

In an embodiment, the oxazoline groups on the reactive polymer, theoxazoline funtionalized polymer, can chemically react with chemicalfunctional groups on keratin fibers and with chemical functional groupson a second compound or polymer. In various embodiments in accordancewith the present invention, the oxazoline groups on the oxazolinefuntionalized polymer chemically react with the amino groups on thepolyamine compound. At the same, in various embodiments in accordancewith the present invention, the oxazoline groups on the oxazolinefuntionalized polymer and/or the amino groups on the polyamine compoundchemically react with chemical functional groups on keratin fibers.

Due to the grafting of the reactive polymer (s) onto keratin fibers,various cosmetic properties can be imparted to the keratin fibers: (i)depending on the type of the reactive polymer (s) and/or (ii) the typeof second compound or polymer with which the reactive polymer hasreacted with and/or (iii) the product resulting from the reactionbetween the reactive polymer and the second compound or polymer. Sincethe reactive polymer (s) (i) or the product (iii) can be firmly fixed onthe keratin fibers, the cosmetic properties provided to the keratinfibers can last for a long time.

By way of non-limiting example only, the oxazoline polymers may beobtained by polymerizing monomers having an oxazoline-type functionalgroup (a non-radical-polymerizable functional group) of the followingformula (I):

R1, R2, R3, and R4 are independently of each other, hydrogen, a halogen,an alkyl, an aryl, alkoxyalkyl or alkoxyaryl, such as an alkyl grouphaving 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms;R5 is an organic group bearing a radical polymerizable vinyl bond,

and when desired, copolymerizing with other one or more kinds ofmonomers, for example, those bearing a vinyl type of bond. The term“vinyl” with respect to a polymeric material means that the materialcomprises repeating units derived from vinyl monomers. As used withrespect to a vinyl monomer, the term “vinyl” means that the monomercontains a moiety having a free-radically polymerizable carbon-carbondouble bond. Monomers having such moieties are capable ofcopolymerization with each other via the carbon-carbon double bonds.

By way of non-limiting examples, the oxazoline functional monomers ofthe present invention as represented by the above formula (I) include2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline,2-vinyl-4-dimethyl-2-oxazoline, 2-vinyl 4-diethyl-2-oxazoline,2-vinyl-4-methoxy-2-oxazoline, 2-vinyl-4-ethoxy-2-oxazoline,2-vinyl-4-methoxy-methyl-2-oxazoline, 2-vinyl -4-phenyl-2-oxazoline,2-vinyl-5-methyl-2-oxazoline, 2-vinyl-5-ethyl-2-oxazoline,2-vinyl-5-dimethyl-2-oxazoline, 2-vinyl-5-methoxy-2-oxazoline,2-vinyl-5-ethoxy-2-oxazoline, 2-vinyl-5-methoxymethyl-2-oxazoline,2-vinyl-5-phenyl-2-oxazoline, 2-vinyl-4-methoxymethyl-5-phenyl-2-oxazoline, 2-isopropenyl-2-oxazoline,2-isopropenyl-4-methyl-2-oxazoline,2-isopropenyl-4-dimethyl-2-oxazoline, 2-isopropenyl-4-diethyl-2-oxazoline, 2-isopropenyl-4-methoxy-2-oxazoline,2-isopropenyl-4-ethoxy-2-oxazoline,2-isopropenyl-4-methoxy-methyl-2-oxazoline,2-isopropenyl-4-phenyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline,2-isopropenyl-5-ethyl-2-oxazoline,2-isopropenyl-5-dimethyl-2-oxazoline,2-isopropenyl-5-methoxy-2-oxazoline, 2-isopropenyl-5-ethoxy-2-oxazoline,2-isopropenyl-5-methoxy-methyl-2-oxazoline,2-isopropenyl-5-phenyl-2-oxazoline,2-isopropenyl-4-methoxymethyl-5-phenyl-2-oxazoline, and the like as aspecific example.

The vinyl monomers can be chosen from, (meth)acrylate monomers,(meth)acrylamide monomers. The term “(meth)acryl” and variationsthereof, as used herein, means acryl or methacryl.

The (meth)acrylate monomers may be, by way of non-limiting example,C1-C8 alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl(meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl(meth)acrylate, tert-butyl (meth)acrylate, pentyl(meth) acrylate,isopentyl (meth)acrylate, neopentyl (meth)acrylate, hexyl(meth)acrylate, isohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,cyclohexyl (meth)acrylate, isohexyl (meth)acrylate, heptyl(meth)acrylate, isoheptyl (meth)acrylate, octyl (meth)acrylate, isooctyl(meth)acrylate, allyl (meth)acrylate, and combinations thereof.Additional and non-limiting examples include C1-08 alkoxy(meth)acrylates, such as methoxy (meth)acrylate, ethoxy (meth)acrylate,propyl oxide (meth)acrylate, isopropyl oxide (meth)acrylate, butyl oxide(meth)acrylate, tert-butyl oxide (meth)acrylate, pentyl oxide (meth)acrylate, isopentyl oxide (meth)acrylate, neopentyl oxide(meth)acrylate. The esters may be, by way of non-limiting example, C2-C6hydroxy alkyl (meth)acrylates, such as hydroxy ethyl (meth)acrylate,2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, ethylene glycoldi(meth)acrylate, polyethylene glycol mono(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6,hexane diol di(meth)acrylate, and anycombination thereof. The esters may be, by way of non-limiting example,aryl (meth)acrylates such as benzyl (meth)acrylate, phenyl(meth)acrylate, and any combination thereof. The esters can furthercontain amino groups such as aminoethyl (meth)acrylate,N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate, N,N-dimethylaminodimethylpropyl (meth)acrylate,N,N-diethyleaminoethyl (meth)acrylate, and N,N,N-trimethylaminoethyl(meth)acrylate; and salts of the ethylenic amines.

According to at least certain exemplary embodiments, the alkyl group ofthe esters may be either fluorinated or perfluorinated, e.g. some or allof the hydrogen atoms of the alkyl group are substituted with fluorineatoms. The monomers can also be fluorine-containing monomers, such as,by way of non-limiting example, trifluoroethyl methacrylate,2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,4,4-hexafluorobutylmethacrylate, perfluorooctyl methacrylate and perfluorooctyl acrylate;and silicone macromonomers.

The amides of (meth)acrylic monomers can, for example, be made of(meth)acrylamides, and especially N-alkyl (meth)acrylamides, inparticular N-(C1-C12) alkyl (meth)acrylates such as N-ethyl(meth)acrylamide, N-t-butyl (meth)acrylamide, N-t-octyl(meth)acrylamide, N-methylol (meth)acrylamide and N-diacetone(meth)acrylamide, and any combination thereof.

The vinyl monomers can include, but are not limited to, vinyl cyanidecompounds such as acrylonitrile and methacrylonitrile; vinyl esters suchas vinyl formate, vinyl acetate, vinyl propionate, vinyl neodecanoate,vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate, triallylcyanurate; vinyl halides such as vinyl chloride and vinylidene chloride;aromatic mono- or divinyl compounds such as styrene, a-methylstyrene,chlorostyrene, alkylstyrene, divinylbenzene and diallyl phthalate, andcombination thereof. Other non-limiting ionic monomers can includepara-styrensulfonic, vinylsulfonic, 2-(meth)acryloyloxyethylsulfonic,2-(meth)acrylamido-2-methylpropylsulfonic acids.

The vinyl monomers can also include the monomers of formulas (II) to(VIII) as described in the PCT publication, WO 2012/099110.

The list of monomers given is not limiting, and it should be understoodthat it is possible to use any monomer known to those skilled in the artwhich includes acrylic and/or vinyl monomers (including monomersmodified with a silicone chain).

In an embodiment, the oxazoline groups on the reactive polymer(oxazoline funtionalized polymer of the present invention) chemicallyreact with chemical functional groups on keratin fibers such as hair andwith the functional groups on another compound of the present invention,in this case, the polyamine compound.

In an embodiment, the oxazoline functionalized polymers of the presentinvention are commercially available under the tradename of EPOCROS, assold by Nippon Shokubai. In an embodiment, the oxazoline funtionalizedpolymers of the present invention are waterborne cross linker polymers.In an embodiment, the oxazoline funtionalized polymers of the presentinvention are of the granule type.

As used herein, the term “waterborne polymer” means that the polymer issoluble or dispersible or emulsifiable in water.

In an embodiment, when the oxazoline funtionalized polymers are chosenfrom waterborne crosslinker polymers, said polymers includeacrylic-based polymers (main component is of the acrylic type) andstyrene/acrylic-based polymers (main component is of the styrene/acrylictype).

In an embodiment, the oxazoline functionalized polymers for use inaccordance with the present invention are waterborne crosslinker polymerwhich are reactive with amino groups. The rate of reaction can beincreased at temperatures above room temperature.

In an embodiment, the oxazoline functionalized polymers for use inaccordance with the present invention are waterborne crosslinkerpolymers which are reactive with the thiol or hydroxyl group on anaromatic ring, thereby forming amide ester bonds.

For example and without limitation, the at least one oxazolinefunctionalized polymer is chosen from the oxazoline functionalizedpolymers sold under the commercial names of EPOCROS WS-300, EPOCROSWS-500, and EPOCROS WS-700 (water-soluble type and acrylic-based), theoxazoline funtionalized polymers sold under the commercial names ofEPOCROS K-2010-E, K-2020-E, and EPOCROS K-2030-E (emulsion type andstyrene/acrylic-based), and a mixture thereof. The oxazolinefunctionalized polymer in EPOCROS WS-300 has the chemical name:2-Propenoic acid, 2-methyl-, methyl ester, polymer with4,5-dihydro-2-(1-methylethenyl)oxazole and ethyl 2-propenoate, withformula: (C₆—H₉—N—O.C₅—H₈—O₂.C₅—H₈—O₂)_(x). The oxazoline functionalizedpolymer in EPOCROS K-2020-E and K-2030-E has the chemical name:styrene.butylacrylate.2-isopropenyl-2-oxazoline.divinyl benzenecopolymer, with formula: (C₇—H₁₂—O₂.C₈.C₁₀—H₁₀.—C₆—H₉—N—O)_(x).

In other examples, the at least one oxazoline functionalized polymer ischosen from the granule type sold under the commercial names of EPOCROSRPS-1005.

The at least one oxazoline functionalized polymer of the presentinvention may, for example, be present in the composition (one treatmentcomposition or composition resulting from a layer by layer application)containing the at least one oxazoline functionalized polymer and the atleast one polyamine compound of the present invention in an amountranging from about 0.1% to about 20% by weight, such as from about 0.5%to about 10% by weight, or from about 0.7% to about 5% by weight,including all ranges and sub-ranges there between, based on the totalweight of the composition.

In various embodiments, the amount of the at least one oxazolinefunctionalized polymer in the composition (one treatment composition orcomposition resulting from a layer by layer application) containing theat least one oxazoline functionalized polymer and the at least onepolyamine compound of the present invention is about: 0.1%, 0.2%, 0.3%,0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%,1.1 %, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%,2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%,3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%,4.7%, 4.8%, 4.9%, or 5% by weight, based on the total weight of thecomposition, including all ranges with any of these amounts beingendpoints.

In various embodiments, the at least one oxazoline functionalizedpolymer of the present invention may, for example, be present in a firsttreatment composition in an amount ranging from about 0.1% to about 20%by weight, such as from about 0.5% to about 10% by weight, or from about0.7% to about 5% by weight, including all ranges and sub-ranges therebetween, based on the total weight of the first treatment composition,including all ranges with any of these amounts being endpoints. Forexample, the amount of the at least one oxazoline functionalized polymerin the first treatment composition of the present invention is about:0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 0.5%, 0.6%, 0.7%,0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%,2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%,3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%,4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, or 5% by weight, based on the totalweight of the first treatment composition, including all ranges with anyof these amounts being endpoints.

Polyamine Compounds

According to various exemplary embodiments of the disclosure, thecompositions and systems according to the disclosure comprise at leastone polyamine compound.

The polyamine compound of the present disclosure is chosen fromnon-alkoylated polyamines, alkoxylated polyamines, and mixtures thereof.In certain embodiments, the polyamine compounds of the presentdisclosure do not contain silicon atoms or silicone moieties.

Non-Alkoxylated Polyamines

The non-alkoxylated polyamines may in particular be chosen frompolyvinylamines, aminated polysaccharides, amine substitutedpolyalkylene glycols, amine substituted polyacrylate crosspolymers,amine substituted polyacrylates, amine substituted polymethacrylates,proteins, protein derivatives, amine substituted polyesters, polyaminoacids, polyalkylamines, diethylene triamine, triethylenetetramine,spermidine, spermine, and mixtures thereof. The non-alkoxylatedpolyamines for use in the present disclosure can also be chosen fromaminosilicones having at least two amino groups.

The non-alkoxylated polyamines may be chosen from amine-containingpolymers, in particular having a weight-average molecular weight rangingfrom 500 to 1,000,000, preferably ranging from 500 to 500,000, andpreferentially ranging from 500 to 100,000. As amine-comprising polymer,use may be made of polyamines such as poly((C2-C5)alkyleneimines), andin particular polyethyleneimines and polypropyleneimines, especiallypoly(ethyleneimine)s; poly(allylamine); polyvinylamines and copolymersthereof, in particular with vinylamides; polyamino acids which have NH2groups; aminodextran; amino polyvinyl alcohol;acrylamidopropylamine-based copolymers; and chitosans.

The non-alkoxylated polyamines of the present disclosure are alsopreferably chosen from polyvinylamines which are generally sold underthe trade name LUPAMINE or LUVIQUAT from BASF. One preferred example ofsuch non-alkoxylated polyamines are polyvinylamines sold under theLUVIQUAT series such as Vinylamine/vinylformamide copolymer (INCI name),sold as LUVIQUAT 9030 by BASF.

The non-alkoxylated polyamines of the present disclosure may also bechosen from Vinylamine/Vinyl Alcohol Copolymer (INCI name).

Other preferred non-alkoxylated polyamines of the present disclosureinclude are amine substituted polyalkylene glycols such as PEG-15cocopolyamine and PEG-15 Tallow Polyamine and amine substitutedpolyacrylate crosspolymer such as the product sold under the nameCARBOPOL AQUA CC polymer by Lubrizol Advanced Materials, Inc.

The non-alkoxylated polyamine compound of the present disclosure mayalso be chosen from proteins and protein derivatives such as wheatprotein, soy protein, oat protein, collagen, and keratin protein.

In an embodiment of the present disclosure, the non-alkoxylatedpolyamine compound is chosen from polyamino acid compounds comprisinglysine, compounds comprising arginine, compounds comprising histidine,and compounds comprising hydroxylysine. Non limiting examples includechitosan and polyamino acids such as polyarginine, polyhistidine,polylysine, and mixtures thereof.

Alkoxylated Polyamines

The alkoxylated polyamines of the present disclosure are chosen fromamine compounds having at least two amino groups and at least one degreeof alkoxylation. The alkoxylation is provided by an alkylene oxide groupwhich is preferably chosen from ethylene oxide and propylene oxide.

Non-limiting preferred examples of suitable alkoxylated polyaminesinclude compounds corresponding to formula (IB):

NH₂R(R′CHCH₂O)_(x)(R′CHCH₂O)_(y)(R′CHCH₂O)_(z)RNH₂   (IB)

wherein R represents a —CH₂—, —CH₂CH₂—, —CHCH₃—or —C(CH₃)₂— group, or ahydrocarbon radical containing at least 3 carbon atoms that is linear orbranched, acyclic or cyclic, saturated or unsaturated, aliphatic oraromatic, substituted or unsubstituted;

x, y, and z independently of one another, represent numbers of from 0 toabout 100;

R′ represents hydrogen, or an alkyl group, preferably a methyl group;and

the sum of x+y+z is at least 1.

In formula (IB), R is preferably a linear or branched, acyclic alkyl oralkenyl group or an alkyl phenyl group; x, y, and z independently of oneanother, preferably represent numbers ranging from 2 to 100.

Examples of the alkoxylated polyamines for use in the present disclosurewhich correspond to formula (IB) include, for example,tetradecyloxypropyl-1,3-diaminopropane; a C12-14 alkyloxypropyl-1,3-diaminopropane; a C12-15 alkyloxypropyl amine and othersimilar materials that are commercially available from Tomah under thetradename of TOMAH DA-17.

Other examples of alkoxylated polyamines of Formula (IB) are diaminecompounds belonging to the JEFFAMINE series such as the JEFFAMINE D andJEFFAMINE ED series available from Huntsman Corporation, Salt Lake City,Utah. Examples of these Jeffamine compounds are JEFFAMINE D230,JEFFAMINE D400, JEFFAMINE D2000, JEFFAMINE D4000, JEFFAMINE HK-511,JEFFAMINE ED600, JEFFAMINE ED900, and JEFFAMINE ED2003. JEFFAMINE Dseries compounds are amine terminated PPGs (polypropylene glycols) andJEFFAMINE ED series compounds are polyether diamine based with apredominantly PEG (polyethylene glycol) backbone.

Other non-limiting preferred examples of suitable alkoxylated polyaminesin the diamine form include compounds corresponding to formula (IIB):

NH₂(CH₂)_(x)OCH₂CH₂O(CH₂)_(x)NH₂   (IIB)

wherein x is 2 or 3.

Examples of alkoxylated polyamines of Formula (IIB) are diaminecompounds belonging to the JEFFAMINE series available from HuntsmanCorporation, Salt Lake City, Utah, such as JEFFAMINE EDR148, andJEFFAMINE EDR176.

Additional non-limiting preferred examples of alkoxylated polyamines inthe triamine form include compounds corresponding to formula (IIIB):

wherein R is hydrogen, —CH₂ or —C₂H₅,

n=0 or 1, and

x, y, and z independently of one another, represent numbers of from 0 to100 and the sum of x+y+z is at least 1.

Examples of alkoxylated polyamines for use in the present disclosurewhich correspond to formula (IIIB) are triamine compounds belonging tothe JEFFAMINE series such as the JEFFAMINE T series available fromHuntsman Corporation, Salt Lake City, Utah. Examples of the JEFFAMINE Tseries compounds are JEFFAMINE T403, JEFFAMINE T3000, and JEFFAMINET5000. JEFFAMINE T series compounds are triamines made by reacting POwith a triol initiator followed by aminating the terminal hydroxylgroups.

Another type of preferred alkoxylated polyamines include compounds offormulas (IVB) and (VB) hereunder:

wherein

R in formula (IVB) represents the alkyl group derived from tallow and Rin formula (VB) represents the alkyl group derived from coconut oil;

n in both formulas (IVB) and (VB) has a total value ranging from 10 to20;

m in both formulas (IVB) and (VB) has a value ranging from 2 to 6; and

x in both formulas (IVB) and (VB) has a value ranging from 2 to 4.

One particular triamine alkoylated polyamine compound is JEFFAMINE T-500polyetheramine of the formula:

Other preferred types of alkoxylated polyamines include aminosiliconeswith at least one degree of alkoxylation.

Preferred examples of alkoxylated polyamines for use in the presentdisclosure include compounds of Formulas (IVB), (VB) and (VIB) above,such as PEG-Tallow Polyamine, PEG-15 Cocopolyamine, and JEFFAMINE T-500polyetheramine, respectively.

In one preferred embodiment of the present disclosure, the polyaminecompound of the present disclosure is chosen from polyvinylamines suchas Vinylamine/vinylformamide copolymer (INCI name), sold as LUVIQUAT9030 by BASF; alkoxylated polyamines which correspond to formula (IIIB)such as JEFFAMINE T403, JEFFAMINE T3000, and JEFFAMINE T5000 (inparticular, corresponds to formula (VIB); and mixtures, thereof.

The at least one polyamine compound of the present invention may, forexample, be present in the composition (one treatment composition orcomposition resulting from a layer by layer application) containing theat least one oxazoline functionalized polymer and the at least onepolyamine compound of the present invention in an amount ranging fromfrom about 0.001% to about 20% by weight, such as from about 0.003% toabout 5% by weight, from about 0.004% to about 5% by weight, or fromabout 0.09% to about 3% by weight, including all ranges and sub-rangesthere between, based on the total weight of the composition.

In various embodiments, the amount of the at least one polyaminecompound in the composition (one treatment composition or compositionresulting from a layer by layer application) containing the at least oneoxazoline functionalized polymer and the at least one polyamine compoundof the present invention is about: 0.002%, 0.004%, 0.005%, 0.006%,0.008%, 0.01%, 0.013%, 0.014%, 0.016%, 0.017%, 0.02%, 0.04%, 0.05%,0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%,0.16%, 0.17%, 0.18%, 0.19%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%,0.9%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%,1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%,2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%,4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, or 5%,byweight, based on the total weight of the composition, including allranges with any of these amounts being endpoints.

In various embodiments, the at least one polyamine compound of thepresent invention may, for example, be present in a second treatmentcomposition in an amount ranging from about 0.04%to about 20% by weight,such as from about 0.05% to about 15% by weight, or from about 0.09% toabout 10% by weight, including all ranges and sub-ranges there between,based on the total weight of the second treatment composition, includingall ranges with any of these amounts being endpoints. For example, theamount of the at least one polyamine compound in the second treatmentcomposition of the present invention is about: 0.05%, 0.06%, 0.07%,0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%,0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%,1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%,2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.2%, 5.4%, 5.5%,5.6%, 5.8%, 6%, 6.2%, 6.4%, 6.5%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.5%,7.6%, 7.8, 8%, 8.2%, 8.4%, 8.5%, 8.6%, 8.8%, 9%, 9.2%, 9.4%, 9.5%, 9.6%,9.8%, 10%, 12%, 14%, 15%, 16%, 18%, or 20% by weight, based on the totalweight of the second treatment composition, including all ranges withany of these amounts being endpoints.

Additional Components

The compositions and systems according to the disclosure may optionallycontain additional components and/or additives, such as solvents, hairactive agents, conditioning agents, and any additional componentsuitable for treatment of keratinous fibers according to the disclosure.

Solvents

In various embodiments, the compositions and systems further compriseone or more suitable solvents for treatment of keratinous fibers.Examples of suitable solvents include water, in some particularembodiments distilled or de-ionised water, organic solvents, or mixturesthereof. Exemplary organic solvents may be chosen from volatile andnonvolatile organic solvents.

Suitable organic solvents are typically C1-C4 lower alcohols, glycols,polyols, polyol ethers, hydrocarbons, and oils. Examples of organicsolvents include, but are not limited to, ethanol, isopropyl alcohol,benzyl alcohol, phenyl ethyl alcohol, propylene glycol, pentyleneglycol, hexylene glycol, glycerol, and mixtures thereof.

Other suitable organic solvents include glycol ethers, for example,ethylene glycol and its ethers such as ethylene glycol monomethyl ether,ethylene glycol monopropyl ether, ethylene glycol monobutyl ether,propylene glycol and its ethers, such as propylene glycol monomethylether, propylene glycol monopropyl ether, propylene glycol monobutylether, dipropylene glycol and diethylene glycol alkyl ethers, such asdiethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, anddipropylene glycol n-butyl ether. Glycol ethers are commerciallyavailable from The Dow Chemical Company under the DOW E-series and DOWP-series. In an exemplary embodiment, glycol ether for use in thepresent invention is dipropylene glycol n-butyl ether, known under thetradename of DOWANOL DPnB.

Suitable organic solvents also include synthetic oils and hydrocarbonoils include mineral oil, petrolatum, and C10-C40 hydrocarbons which maybe aliphatic (with a straight, branched or cyclic chain), aromatic,arylaliphatic such as paraffins, iso-paraffins, isododecanes, aromatichydrocarbons, polybutene, hydrogenated polyisobutene, hydrogenatedpolydecene, polydecene, squalene, petrolatum and isoparaffins, siliconeoils, fluoro oils and mixtures, thereof.

The term “hydrocarbon based oil” or “hydrocarbon oil” refers to oilmainly containing hydrogen and carbon atoms and possibly oxygen,nitrogen, sulfur and/or phosphorus atoms. Representative examples ofhydrocarbon based oils include oils containing from 8 to 16 carbonatoms, and especially branched C8-C16 alkanes (also known asisoparaffins), for instance isododecane (also known as 2,2,4,4,6pentamethylheptane), isodecane and isohexadecane.

Examples of silicone oils that may be useful in the present inventioninclude nonvolatile silicone oils such as polydimethylsiloxanes (PDMS),polydimethylsiloxanes comprising alkyl or alkoxy groups that are pendentand/or at the end of a silicone chain, these groups each containing from2 to 24 carbon atoms, phenyl silicones, for instance phenyltrimethicones, phenyl dimethicones, phenyl trimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyltrisiloxanes and 2 phenylethyl trimethylsiloxysilicates, anddimethicones or phenyltrimethicones with a viscosity of less than orequal to 100 cSt.

Other representative examples of silicone oils that may be useful in thepresent invention include volatile silicone oils such as linear orcyclic silicone oils, and especially containing from 2 to 10 siliconatoms and in particular from 2 to 7 silicon atoms, these siliconesoptionally comprising alkyl or alkoxy groups containing from 1 to 10carbon atoms. Specific examples include dimethicones with a viscosity of5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane,heptamethyloctyltri-siloxane, hexamethyldisiloxane,octamethyltrisiloxane, decamethyltetrasiloxane anddodecamethylpentasiloxane, and mixtures thereof.

Representative examples of fluoro oils that may be suitable for use inthe present invention include volatile fluoro oils such asnonafluoromethoxybutane and perfluoro methylcyclopentane.

Particularly suitable solvents in the composition of the presentdisclosure include water, isododecane, ethanol, and combinationsthereof. The solvent will typically be present in total amounts rangingfrom about 60% to 98%, in some particular embodiments from 80% to 96%,by weight, including all ranges and sub-ranges there between, based onthe total weight of the composition.

In yet some other embodiments, the solvent of the present disclosuredoes not comprise water and/or organic solvent that is added as aseparate ingredient, by itself, into the compositions of the presentinvention, such that water and/or organic solvent is present in thecompositions of the present invention when it accompanies one or moreingredients of a raw material that is added into the compositions of theinvention.

When the compositions of the disclosure contain water, according tovarious embodiments, water can be present in amounts of about 98% orless, such as about 96%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%,50%, 48%, 46%, 45%, 44%, 42%,40%, 35%,30%, 20%, 10%, or 5% or less, byweight, based on the total weight of the composition, including allranges with any of these amounts as endpoints.

When the compositions of the disclosure contain an organic solvent(s),according to various embodiments, the organic solvent(s) can be presentin a total amount of about 98% or less, such as about 96%, 95%, 90%,85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 48%, 46%, 45%, 44%, 42%, 40%,35%, 30%, 20%, 10%, or 5%, or less, by weight, based on the total weightof the composition, including all ranges with any of these amounts asendpoints.

Conditioning Agents and Compositions

The compositions and systems for treating keratinous fibers inaccordance with the present disclosure may optionally compriseconditioning compositions or conditioning agents other than thepolyamine compounds of the present invention, such as cationicconditioning agents, silicone compounds, and mixtures thereof.

The total amount of the one or more conditioning agents may vary. Insome cases, the total amount of the one or more conditioning agents isfrom about 0.1 to about 25 wt. %, about 0.1 to about 20 wt. %, about 0.1to about 15 wt. %, 0.1 to about 10 wt. %, 0.1 to about 5 wt. %, about 1to about 25 wt. %, about 1 to about 20 wt. %, about 1 to about 15 wt. %,about 1 to about 10 wt. %, or about 1 to about 5 wt. %, based on thetotal weight of the composition.

In some embodiments, the total amount of the one or more conditioningagents in the composition ranges from about 0.1 to about 5% by weight,about 0.2 to about 4% by weight, about 0.4 to about 3% by weight, about0.5 to about 2% by weight, or about 0.5 to about 1% by weight, based onthe total weight of the conditioning composition, including all rangesand sub-ranges there between. In a particular embodiment, the amount ofthe silicone compound is at about 0.4%, 0.43%, 0.45%, 0.5%, 0.55%,0.57%, 0.6%, 0.65%, 0.7%, 0.75%, 0.78%, 0.8%, 0.85%, 0.9%, 0.95%, 1%,1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%,2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%,3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% by weight, based on the total weight ofthe conditioning composition, including all ranges with any of theseamounts as endpoints.

Additives

The compositions and systems according to the present disclosure mayoptionally further include suitable additives for treatment ofkeratinous fibers. For example, the compositions and systems may alsocomprise additives chosen from emulsifiers/co-emulsifiers, rheologymodifiers, thickening and/or viscosity modifying agents, nacreousagents, opacifiers, fragrances, vitamins, preserving agents,neutralizing agents, pH stabilizers, and mixtures thereof.

Suitable examples of emulsifiers are nonionic surfactants such asalkoxylated fatty alcohols, fatty alcohols, fatty amides, sorbitanderivatives, polyethylene glycol esters (e.g., PEG-100 stearate), andmixtures thereof.

If present in the composition, the above-described additives aregenerally present in an amount ranging up to about 50% by weightincluding all ranges and sub-ranges there between, based on the totalweight of the composition, such as from about 0.001% to about 50%, orfrom about 0.001% to about 40%, or from about 0.001% to about 30%, orfrom about 0.001% to about 20%, or from about 0.001% to about 10%, byweight, based on the total weight of the composition.

Needless to say, a person skilled in the art will take care to selectthis or these optional additional components or additives, and/or theamount thereof, such that the advantageous properties of thecomposition, according to the invention, are not, or are notsubstantially, adversely affected by the envisaged addition.

Compositions, Systems, and Methods of Use

According to various embodiments of the disclosure, the treatmentcompositions may be a single-composition treatment, or may be atwo-composition treatment system. In various embodiments, the presentdisclosure is also directed to methods of treating hair, the methodscomprising applying compositions and systems according to the disclosureonto keratinous fibers such as hair. The treatment process may thus be aone-step or two-step application.

For example, in one exemplary and non-limiting embodiment, the presentdisclosure is directed to compositions for the treatment of keratinousfibers such as hair, wherein a single composition comprises at least oneoxazoline functionalized polymer and at least one polyamine compound. Insuch embodiments, the composition of the present disclosure is appliedonto keratinous fibers such as hair in a one-step application process.The composition for use in a one-step application may be prepared bycombining the at least one oxazoline functionalized polymer and the atleast one polyamine compound, resulting in a treatment composition thatis then applied onto the keratinous fibers.

In yet a further exemplary and non-limiting embodiment, the presentdisclosure is directed to a system comprising two compositions: (a) afirst treatment composition containing at least one oxazolinefunctionalized polymer; and (b) a second treatment compositioncontaining at least one polyamine compound, wherein (a) and (b) are tobe applied sequentially onto hair in any order or are to be combined toform a hair treatment mixture for application onto hair.

In exemplary embodiments, keratinous fibers such as hair are treated ina two-step application process, i.e., the fibers are treated by systemcomprised of two treatment compositions. In one exemplary andnon-limiting embodiment of the two-step application process, twotreatment compositions are applied to the keratinous fibers in astep-wise fashion in any order to treat the substrate, wherein a firsttreatment composition contains the at least one oxazoline functionalizedpolymer, and a second treatment composition contains the at least onepolyamine compound.

In exemplary embodiments, the above-described first or second treatmentcompositions or hair treatment mixture are heat-activated compositionssuch that certain cosmetic benefits are imparted to hair fibers when thefibers are heated at a temperature above room temperature before orduring or after treating the hair with the said composition(s) ormixture.

As described herein, heating of keratinous fibers may be effected byapplying heat to the hair or exposing hair to elevated temperatures ortemperatures above room temperature. The temperature of heating can beequal to or above 30° C., equal to or above 40° C., equal to or above45° C., equal to or above 50° C., equal to or above 55° C., equal to orabove 60° C., equal to or above 70° C., equal to or above 80° C., equalto or above 90° C., equal to or above 100° C., equal to or above 125°C., equal to or above 150° C., equal to or above 175° C., equal to orabove 200° C., or equal to or above 225° C., including all ranges oftemperatures having any of these numbers as endpoints. While not solimited, heating may be provided, for example, by commonly used heatingtools for example a heating lamp or helmet dryer or blow dryer (about30° C. and above, such as from about 30° C. to about 100° C. or fromabout 40° C. to about 80° C. or from about 40° C. to about 70° C.) orhot iron or flat iron (about 130° C. to about 250° C.) or steam/hotrollers. Heating the hair may be accompanied by the use of a brush orcomb or similar device over the fibers or by running the fingers throughthe fibers. When a flat iron is employed, one or more several passes ofthe flat iron over the fibers are employed.

In various exemplary embodiments, the weight ratio of the at least oneoxazoline functionalized polymer to the at least one polyamine compoundin the compositions and systems of the disclosure can range from about20:1 to 1:2, such as from about 18:1 to about 1:2, about 16:1 to about1:2, about 15:1 to about 1:2, about 14:1 to about 1:2, about 12:1 toabout 1:2, about 10:1 to about 1:2, about 9:1 to about 1:1, about 8:1 toabout 1:1, about 7:1 to about 1:1, about 6.5:1 to about 1:1, about 6.25to about 1:1, about 6:1 to about 1:1, about 5:1 to about 1:1, about 4:1to about 1:1, about 3:1 to about 1:1, or about 2:1 to about 1:1,including ranges and sub-ranges there between. For example, the weightratio of the at least one polyamine compound to the oxazolinefunctionalized polymer is at about: 20, 18, 16, 15, 14, 12, 10, 9.7, 9,8, 7, 6.9, 6.5, 6.25, 6, 5.5, 6, 5, 4, 4.3, 3, 2, 2.2, 1, 0.9, 0.8, 0.7,0.6, or 0.5, including all ranges with any of these amounts beingendpoints. In certain embodiments, the at least one oxazolinefunctionalized polymer is present in a greater proportion than thepolyamine compound. In certain other embodiments, the at least oneoxazoline functionalized polymer is present in a lesser proportion thanthe polyamine compound.

In various embodiments, the present disclosure is directed to hairtreatment systems comprising at least: a first composition containing atleast one oxazoline functionalized polymer and a solvent; and a secondcomposition containing at least one polyamine compound and a solvent;wherein the first and the second compositions are each contained inseparate containers and wherein the first and the second compositionsare applied on hair in a step-wise manner.

In one exemplary embodiment, the first and second treatment compositionsabove may be applied to keratinous fibers, such as hair, according to atwo-step application method comprising steps of:

-   -   (i) applying the first treatment composition onto the fibers;    -   (ii) leaving the first treatment composition on the fibers at        room temperature for a certain period of time, such as for at        least 30 seconds such as from about 1 to about 60 minutes, or        about 40 minutes to about 60 minutes, or for about 10 minutes or        about 15 minutes or about 20 minutes or about 25 minutes or        about 30 minutes or about 35 minutes or about 40 minutes or        about 60 minutes;    -   (iii) applying the second treatment composition onto the fibers;    -   (iv) leaving the first treatment composition on the fibers at        room temperature for a certain period of time, such as for at        least 30 seconds such as from about 1 to about 60 minutes, or        about 40 minutes to about 60 minutes, or for about 10 minutes or        about 15 minutes or about 20 minutes or about 25 minutes or        about 30 minutes or about 35 minutes or about 40 minutes or        about 60 minutes; and    -   (v) optionally, heating the fibers at a temperature above room        temperature.

In one exemplary embodiment, the disclosure relates to a single-steptreatment composition comprising at least one oxazoline functionalizedpolymer and a solvent; a second composition containing at least onepolyamine compound; and a solvent.

In one exemplary embodiment, the single composition above may be appliedto keratinous fibers, such as hair, according to a single-stepapplication method comprising steps of:

(i) applying the treatment composition onto the fibers;

(ii) leaving the first treatment composition on the fibers at roomtemperature for a certain period of time, such as for at least 30seconds such as from about 1 to about 60 minutes, or about 40 minutes toabout 60 minutes, or for about 10 minutes or about 15 minutes or about20 minutes or about 25 minutes or about 30 minutes or about 35 minutesor about 40 minutes or about 60 minutes; and

-   -   (iii) optionally, heating the fibers at a temperature above room        temperature.

In some embodiments, the hair that has been treated with thecompositions of the present invention and then heated is rinsed withwater and/or a shampoo and or a conditioner.

In at least some embodiments, the compositions and systems for treatingkeratinous fibers, such as hair fibers, according to the disclosureincludes amounts of each of the at least one oxazoline functionalizedpolymer and the at least one polyamine compound, sufficient to impart tothe keratinous fibers after application thereto, one or more of:

hydrophobicity or increased hydrophobicity;

humidity resistance;

increased manageability;

frizz-control or improved frizz control;

durable frizz control;

improved conditioning;

protection from damage caused by extrinsic and/or intrinsic factors;

repair when the keratinous fibers are in a damaged condition;

minimized or no breakage;

increased or improved mechanical strength; or

increased hold to the shape or configuration of the fibers.

The compositions and methods, according to the present disclosure,provides advantageous properties to keratinous fibers. In oneembodiment, the compositions and methods, according to the presentdisclosure, provide or impart hydrophobicity to hydrophilic or damagedkeratinous fibers, such as damaged hair (bleached), upon applicationthereto. In certain embodiments, hydrophobicity is provided at roomtemperature, i.e., without heating or applying heat to the hair. Inother embodiments, the hydrophobicity is provided when heat is used onthe hair (before or after applying the composition(s) on the hair orduring the application of the composition(s) on the hair).

In one embodiment, the hydrophobicity provided to less hydrophobic or tohydrophilic keratinous fibers includes a contact angle of greater than85° or greater than 90° or greater than 95° or greater than100° orgreater than 110° or greater than 120° or ranges from between 85° to140° or from between 90° to 135° or from between 100° to 130°, includingranges and sub-ranges there between.

Further disclosed herein is the use of the compositions of the presentdisclosure for caring for keratinous fibers, for example, hair, such asfor hair repair treatments, or for reducing damage to the hair or forimparting improved strength to hair or reducing/preventing hairbreakage.

The compositions of the present disclosure may be employed in aneffective amount to adequately cover the surface of the fibers of thehair and to achieve the desired effects of hair repair and conditioning.

An effective amount of the composition is typically from about 0.03 gramto about 50 grams per head of hair, and in some applications fortreatment of hair, in amounts from about 5 to 60 grams, and in yetfurther embodiments for an abundance of hair in amounts from about 10 toabout 80 grams or more. It will thus be appreciated that the amountsapplied depend on the amount or volume of keratinous fibers, such ashair, to be treated and may thus fall within lower ranges for smallamounts or patches of hair to the higher ranges and beyond for largeamounts or patches of hair. Typical applications are to the whole headin the case of treatment of hair. It will be understood that applicationto the hair typically includes working the composition through the hair.

Further disclosed herein is the use of the compositions of the presentdisclosure for shaping or styling hair and/or retaining a hairstyle.Also disclosed is the use of the compositions of the present disclosurefor caring for the hair such as for hair repair treatments, or forreducing damage to the hair or for improving the feel of the hair byimparting hydrophobicity to the hair. The compositions may be applied towet or dry hair. They may be used in a non-rinse fashion. In some otherembodiments, the composition may be rinsed from the hair.

In an embodiment, the hair that has been contacted with the treatmentcompositions and systems of the present invention is further heated orexposed to elevated temperatures (above room temperature). The heatsource can be chosen from a blow dryer, a flat iron, a hair dryer, aheat lamp, a heat wand, or other similar devices.

A smoothing or crimping action may be applied on the hair while heatingthe hair by use of suitable devices, including a hair brush, comb, orflat iron. The smoothing action on the hair may also include running thefingers through the hair.

In an embodiment, the hair treated with the compositions and systems ofthe present invention are heated or subjected to heat or elevatedtemperatures (above room temperature).

A suitable applicator device for contacting the hair with compositionsof the present invention is an applicator brush. It will be appreciatedthat while a brush is an example of a suitable applicator, particularlyfor hair, other applicators may be used, including but not limited tospray bottles, squeeze bottles, one and two chamber pumps, tubes, combs,and other applicators known in the art.

In addition, independently of the embodiment use, the compositionpresent on the fibers or hair is left in place for a time, generally,from about 30 seconds to about 60 minutes, such as from about 40 toabout 60 minutes, or such as from about 5 to about 45 minutes, or suchas from about 5 to about 20 minutes, or such as from about 10 to about20 minutes, or such as of about 20 minutes or such as of about 10minutes. In alternate embodiments, the treatment times may be longer,and in some embodiments, appreciably longer, such that the applicationmay be left on for up to 24 hours to about 48 hours.

The compositions of the present invention are easy to spread on hair.

It has surprisingly and unexpectedly discovered that the application ofthe composition onto hair results in less frizzy hair and/or moreconditioned hair and/or more humidity resistant hair. It was alsosurprisingly and unexpectedly discovered that the application of thecomposition of the present invention onto the hair resulted in improvedhair quality, for example, one or more of better hair feel, less frizzyhair, less damaged feel of hair, smoother hair, better hairmanageability, or improved appearance of the hair (e.g., healthy look).

The hair care and hair cosmetic effects obtained using the compositionsand methods of the present invention may also be durable orlong-lasting, i.e., wash or shampoo resistant.

As used herein, “long-lasting” or “durable” is understood to mean thatthe benefits imparted to hair by the compositions of the invention lastover a period of time and/or over high humidity conditions and/or afterone or multiple wash cycles (with water or shampoo/water orshampoo/water/conditioner/water or conditioner/water). The multiple washcycles is understood to mean one or more wash cycles, such as one or twoor three or four or five or six or seven or eight or nine or ten washcycles.

Instructions for applying the composition of the present invention ontokeratinous fibers such as hair on the head may comprise directions ofuse of the composition for the end-user to follow. The end-user may be aconsumer or cosmetologist or salon hair dresser. Directions may compriseinstructing the end-user to take an amount of the composition insufficient quantity such that the composition adequately covers thesubstrates and imparts the desired effects. Directions may additionallyinstruct the end-user to use a device (e.g., heating device) to achievethe desired effects.

Instructions for using the composition(s) of the present invention mayappear on the container (such as can, bottle or jar) holding thecomposition(s) of the present invention or on the box or carton or otherpackaging comprising the container(s) holding the composition(s).

The compositions described above are useful for application ontokeratinous fibers such as hair on the head of human individuals.

Thus, the compositions of the present invention can be made into variouscosmetic products such hair care, hair treatment, and hair stylingproducts.

Representative types of hair care compositions, including hair care andstyling compositions, of the present invention include compositions forconditioning or protecting hair from heat damage, leave-in hairtreatments, rinse-off hair treatments, combination shampoo/stylingcompositions, hair volumizing compositions, compositions for shaping thehair or maintaining the shape of the hair or styling products (e.g.,gels, creams, milks, pastes, waxes, ointments, serums, foams, hairlotions, mousses, pump-sprays, non-aerosol sprays and aerosol sprays).

The compositions of the present invention can be in the form of anaqueous composition or an emulsion, such as a lotion or cream, and insome embodiments may be applied in another form, such as in a serum suchas an anhydrous serum (substantially free of water, for examplecontaining less than 0.1% water or not containing added water to thecomposition).

In one embodiment, the composition of the present invention is in theform of a cream or a lotion or a serum.

In one embodiment, the compositions (first and/or second treatmentcompositions and/or single treatment composition) of the presentinvention are in the form of aqueous compositions or aqueous-alcoholiccompositions.

In one embodiment, the compositions (first and/or second treatmentcompositions and/or single treatment composition) of the presentinvention are in the form of emulsions and further comprise one or moreemulusifiers.

The compositions may be packaged in various forms, especially in a tube,a jar or bottles, in pump bottles, in squeeze bottles, or in aerosolcontainers so as to apply the composition in vaporized form or in theform of a mousse. The compositions may also be impregnated onapplicators, especially gloves or wipes.

The composition may be applied by hand, with an applicator nozzle oractuator pump, with a container equipped with a pump, an applicator anda dispensing comb, or with an insoluble substrate impregnated with thecomposition.

As used herein, the methods and compositions disclosed herein may beused on the hair that has not been artificially dyed, pigmented orpermed.

As used herein, the methods and compositions disclosed herein may bealso used on the hair that has been artificially dyed, pigmented orpermed, relaxed, straightened or other chemical process.

As used herein, the methods and compositions disclosed herein may bealso used on the hair that is undergoing a chemical treatment such as ableaching or lightening treatment or an oxidative dyeing treatment or arelaxing/straightening treatment or a perming/waving treatment.

The compositions according to the disclosure may be prepared accordingto techniques that are well known to those skilled in the art.

Although the foregoing refers to various exemplary embodiments, it willbe understood that the disclosure is not so limited. It will occur tothose of ordinary skill in the art that various modifications may bemade to the disclosed embodiments and that such modifications areintended to be within the scope of the disclosure. Where an embodimentemploying a particular structure and/or configuration is illustrated inthe present disclosure, it is understood that the present disclosure maybe practiced with any other compatible structures and/or configurationsthat are functionally equivalent provided that such substitutions arenot explicitly forbidden or otherwise known to be impossible to one ofordinary skill in the art.

The following examples are intended to further illustrate the presentinvention. They are not intended to limit the invention in any way.Unless otherwise indicated, all parts are by weight.

EXAMPLES

The following examples are to illustrate the invention and arenon-limiting. In accordance with the various examples, the evaluationsand results demonstrate generally that the inventive compositions andmethods confer beneficial results, including improved quality of hairand improvement to the hydrophobicity of the hair, including longlasting or wash-resistant hydrophobicity to hair.

TABLE 1 Representative Actives Raw Material (“RM”) Trade Name oringredient name or INCI name Generic Name EPOCROS K-2030-E, 40 wt. %active, Oxazoline functionalized supplied by Nippon Shokubai polymer AEPOCROS K-2020-E, 40 wt. % active, Oxazoline functionalized supplied byNippon Shokubai polymer B LUVIQUAT (13 wt. % active, INCI name:Polyamine compound VINYLAMINE/VINYLFORMAMIDE COPOLYMER), supplied byBASF

Hydrophobicity Evaluation on Hair Swatches—Contact Angle Measurements

-   Hydrophobicity of each swatch was measured via contact angle    measurements using Biolin Scientific Contact Angle Tensiometer,    Model C204A. A bundle of 30-50 fibers was clamped to create a flat    surface. A 3 μL drop of DI (deionized) H2O was placed on the fiber    surface and the contact angle was measured at 10 seconds. The values    reported below are an average of 3 measurements using the contact    angle at 10 seconds. Natural, undamaged hair is hydrophobic while    damaged hair (double bleached, or platinum bleached) is hydrophilic    and exhibits a contact angle of 0°.

Example 1

Hydrophobicity Assessments on Hair Treated According to a 1-Step System

The following aqueous solutions were prepared:

-   Solution 1: 10.0 wt. % EPOCROS RM containing Oxazoline    functionalized polymer A (40 wt. % active polymer) in water-   Solution 2: 10.0 wt. % LUVIQUAT RM (13 wt. % active    vinylamine/vinylformamide copolymer) in water-   Solution 1 and Solution 2 were combined in a weight ratio of 9:1 in    order to form a mixture or composition (based on 0.36 g of Solution    1/g of hair plus 0.04 g of Solution 2/g of hair resulting in 0.4 g    of the mixture/g of hair).-   Platinum bleached hair swatches from International Hair Importers    (IHIP) (about 2.0 g each) were washed with a hair cleansing cream,    towel dried and treated according to a 1-step application process as    follows:-   The cleansed hair swatches were contacted or treated with the above    mixture or composition containing Solution 1 and Solution 2. The    treated hair was massaged for 30 seconds then combed for 15 seconds    to ensure even distribution of the mixture. The treated swatches    were then heated at about 50° C. for about 40 minutes and air dried    overnight at room temperature (RT).-   Swatches were washed with 0.4 g of a sulfate-based shampoo/1 g hair    and dried. The hydrophobicity of hair (contact angle with the    Tensiometer) was measured (T1). The hair swatches were then    shampooed with the sulfate-based shampoo and washed four more times    (a total of five shampoos or five wash cycles) and the    hydrophobicity of the hair was measured after the swatch was dried    overnight at RT (T5).-   Three measurements (top, middle and end of hair swatch) were    acquired for each sample. The average contact angle is reported in    the table below with the standard deviation from three measurements.

TABLE 2 Average Contact Angle Average Contact Angle Active Ingredient in(°) @ T1 = 1 x (°) @ T5 = 5 x RM Sample Shampoo Shampoo Oxazolinefunctionalized 0.00 0.00 polymer A Polyamine compound  81.55 +/− 1.580.00 Oxazoline functionalized 121.52 +/− 3.16 127.90 +/− 7.73 polymer Aand Polyamine compound combination* *Amino/Oxazoline (mole ratio) =1/10.4

The contact angle measurements above show that the combination ofoxazoline functionalized polymer A with the polyamine compound, resultedin the formation of a coating on the hair which imparted hydrophobicityor improved hydrophobicity to the hair even after the hair has beenshampooed once or five times, i.e., the hydrophobicity imparted to hairwas shampoo or wash resistant. In contrast, the results show that theoxazoline functionalized polymer alone did not impart hydrophobicity tohair as shown by the zero contact angle. In addition, the degree ofhydrophobicity imparted to hair by the polyamine compound alone wassignificantly less than that imparted by the inventive combination ofoxazoline functionalized polymer and polyamine and this effect did notlast after several shampooing or washing cycles as shown by the zerocontact angle at T5.

Summary of Findings: In summary, the treatment of the hair with a systemcomprising an oxazoline functionalized polymer and polyamine compoundconferred hydrophobicity benefits or properties to the hair as comparedto the treatment of the hair with the oxazoline functionalized polymeralone or the polyamine compound alone. The imparted hydrophobicitybenefits were found to be long lasting over several shampooings orshampoo (or wash) resistant.

The treatment composition can also be provided to the hair as a layer bylayer system (2-step system or 2-step application process) involving afirst composition containing an oxazoline functionalized polymer and asecond composition containing a polyamine compound in any sequentialorder.

The present invention may involve various methods of treating hair withcompositions employing various combinations of the oxazolinefunctionalized polymer A or B in Table 1 with vinylamine/vinylformamidecopolymer either as single treatment compositions or according to a2-step or layer by layer application process.

While the invention has been described with reference to certainexemplary or preferred embodiments, it will be understood by thoseskilled in the art that various changes may be made and equivalents maybe substituted for elements thereof without departing from the scope ofthe invention. In addition, many modifications may be made to adapt aparticular situation or material to the teachings of the inventionwithout departing from the essential scope thereof. Therefore, it isintended that the invention not be limited to the particular embodimentdisclosed as the best mode contemplated for carrying out this invention,but that the invention will include all embodiments falling within thescope of the appended claims.

1. A composition for treatment of keratinous fibers comprising: at leastone oxazoline functionalized polymer; and at least one polyaminecompound.
 2. The composition according to claim 1, wherein the at leastone oxazoline functionalized polymer is chosen from a waterbornecrosslinker polymer, a granule type, and a mixture thereof.
 3. Thecomposition according to claim 2, wherein the at least one oxazolinefunctionalized polymer is a waterborne crosslinker polymer is chosenfrom acrylic-based oxazoline functionalized polymers,styrene/acrylic-based oxazoline functionalized polymers, and a mixturethereof.
 4. The composition according to claim 1, wherein the polyaminecompound is chosen from non-alkoxylated polyamines, alkoxylatedpolyamines, and a mixture thereof.
 5. The composition according to claim4, wherein the polyamine compound is a non-alkoxylated polyamine chosenfrom polyvinylamines, aminated polysaccharides, amine substitutedpolyalkylene glycols, amine substituted polyacrylate crosspolymers,amine substituted polyacrylates, amine substituted polymethacrylates,amine substituted polyesters, polyamino acids, polyalkylamines,diethylene triamine, triethylenetetramine, spermidine, spermine,aminosilicones having at least two amino groups, and a mixture thereof.6. The composition according to claim 5, wherein the polyamine compoundis chosen from poyvinylamines.
 7. The composition according to claim 5,wherein the polyamine compound is chosen from alkoxylated polyamines. 8.The composition according to claim 1, wherein the at least one oxazolinefunctionalized polymer is present in a concentration, by weight, of fromabout 0.1% to about 20%, based on the total weight of the composition.9. The composition according to claim 1, wherein the at least onepolyamine compound is present in a concentration, by weight, of fromabout 0.001% to about 20%, based on the total weight of the composition.10. The composition according to claim 1, wherein the mole ratio of theoxazoline group(s) of the at least one oxazoline functionalized polymerto the amino group(s) of the at least one polyamine compound is greaterthan
 1. 11. The composition according to claim 1, wherein the mole ratioof the oxazoline group(s) of the at least one oxazoline functionalizedpolymer to the amino group(s) of the at least one polyamine compound isless than
 1. 12. The composition according to claim 1, wherein the moleratio of the oxazoline group(s) of the at least one oxazolinefunctionalized polymer to the amino group(s) of the at least onepolyamine compound is from between about 80:1 to about 1:80.
 13. Thecomposition according to claim 1, further comprising a solvent selectedfrom water, organic solvents, or a mixture thereof.
 14. The compositionaccording to claim 1, wherein the keratinous fibers include hair, andwherein the composition is formed in-situ on the hair from a step-wiseapplication on the hair of a first composition comprising at least oneoxazoline functionalized polymer and a solvent, and a second compositioncomprising at least one polyamine compound and a solvent, wherein thesolvents in the first and second compositions are independently chosenfrom water, organic solvents, or mixtures thereof.
 15. The compositionaccording to claim 1, wherein the composition includes amounts of eachof the oxazoline functionalized polymer and the polyamine compoundsufficient to impart to the keratinous fibers after application thereto,one or more of hydrophobicity, manageability, and frizz control.
 16. Thecomposition according to claim 15, wherein the hydrophobicity impartedto the keratinous fibers includes a contact angle of greater than 85°.17. The composition according to claim 15, wherein the hydrophobicityimparted to the keratinous fibers confers high humidity curl retentionafter a period of exposure to humidity ranging from about 40% to 90%.18. The composition according to claim 15, wherein the hydrophobicityimparted to the keratinous fibers is durable even after one or more washcycles.
 19. A method of treating keratinous fibers, comprising applyingonto keratinous fibers, the treatment composition of claim
 1. 20. Themethod according to claim 19, comprising a step of heating the fibersduring, before, and/or after the treatment composition is applied ontothe fibers.
 21. The method according to claim 19, wherein the methodimparts to the keratinous fibers after application thereto, one or moreof hydrophobicity, manageability, and frizz control.
 22. The methodaccording to claim 21, wherein the method imparts a hydrophobicity tothe keratinous fibers resulting in a contact angle of greater than 85°.23. A method of imparting hydrophobicity and/or manageability tokeratinous fibers chosen from hair and/or protecting keratinous fiberschosen from hair from extrinsic damage caused by heating, UV radiation,chemical treatment or mechanical stress, or of repairing a keratinousfiber chosen from hair following extrinsic damage caused by heating, UVradiation, chemical treatment, or mechanical stress comprising: applyingto the keratinous fibers a composition according to claim 1; optionallyheating the keratinous fibers; wherein when heating is employed, thecomposition is applied prior to the heating or during the heating orafter the heating.
 24. A method according to claim 23, wherein themethod is a process selected from: a one step process, wherein thecomposition comprising the oxazoline functionalized polymer and thepolyamine compound is provided as a single composition, and is preparedby combining the oxazoline functionalized polymer, the polyaminecompound, and at least a solvent, whereby the single composition isapplied onto the keratinous fibers; a one step process, wherein thecomposition is provided in separate treatment compositions, eachseparately comprising the oxazoline functionalized polymer and thepolyamine compound, the treatment compositions prepared by combining theoxazoline functionalized polymer with at least water to form a firstphase, and separately combining the polyamine compound with at least onea solvent selected from water, organic solvents, or a mixture thereof toform a second phase, whereby at the time of use, the phases are combinedand agitated to form a mixture that is applied onto the keratinousfibers; and a two-step process, wherein the composition is provided inseparate treatment compositions, each separately comprising theoxazoline functionalized polymer and the polyamine compound, thetreatment compositions prepared by combining the oxazolinefunctionalized polymer with water to form a first phase, and separatelycombining the polyamine compound with at least one a solvent selectedfrom water, organic solvents, or a mixture thereof to form a secondphase, whereby at the time of use, each of the phases is appliedseparately to the keratinous fibers in any order.
 25. A system fortreating a keratinous fibers comprising one or two separately-containedtreatment compositions, the system including: (a) at least one oxazolinefunctionalized polymer; and (b) at least one polyamine compound; withthe proviso that either (a) and (b) are each contained in two separatetreatment compositions or (a) and (b) are contained in one treatmentcomposition.
 26. The system according to claim 25, comprising twoseparately-contained treatment compositions comprising: (1) a firsttreatment composition containing: the at least one oxazolinefunctionalized polymer in an amount, by weight, of from about 0.1% toabout 20%, based on the total weight of the first treatment composition;and at least one solvent; and (2) a second treatment compositioncomprising: the at least one polyamine compound, in an amount, byweight, of from about 0.04% to about 20%, based on the total weight ofthe second treatment composition; and at least one solvent.
 27. Thesystem according to claim 25, comprising one treatment compositioncomprising: the at least one oxazoline functionalized polymer in anamount, by weight, of from about 0.1% to about 20%, based on the totalweight of the treatment composition; the at least one polyamine compoundin an amount, by weight, of from about 0.001% to about 20%, based on thetotal weight of the treatment composition.
 28. A method of treatingkeratinous fibers, wherein the method is a two-step process comprisingthe steps of: (i) applying the first treatment composition of claim 26onto the fibers; (ii) applying the second treatment composition of claim26 onto the fibers; and (iii) optionally, heating the fibers at atemperature above room temperature; wherein the keratinous fibersinclude hair.
 29. A method of treating keratinous fibers, comprisingapplying the treatment composition of claim 27 onto the fibers; whereinthe keratinous fibers include hair; and optionally, heating the fibersat a temperature above room temperature.